Quantitative analysis is an area of analytical chemistry used to determine the amount of a species present in a sample. Several methods of quantitative analysis for the hexafluorophosphate ion have been developed. Tetraphenylarsonium chloride, [(C6H5)4As]Cl, has been used both for titrimetric[10] and gravimetric[11] quantifications of hexafluorophosphate. Both of these determinations depend on the formation of tetraphenylarsonium hexafluorophosphate:

Non-coordinating anions are anions that interact only weakly with cations, a useful property when studying highly electrophilic cations.[13] In coordination chemistry, the term can also be used to refer to anions which are unlikely to bind directly to the metal centre of a complex. Hexafluorophosphate is a non-coordinating anion in both senses of the term.[3][4] Three widely used non-coordinating anions are hexafluorophosphate, tetrafluoroborateBF−
4, and perchlorateClO−
4; of these, the hexafluorophosphate ion has the least coordinating ability[14] and it is deliberately used for this property. In the 1990s, a new non-coordinating anion, [B[3,5-(CF3)2C6H3]4]− commonly abbreviated as [BArF4]− and colloquially known as "BARF"[15] was discovered; BARF is far less coordinating than hexafluorophosphate.[16]

Practical uses of the hexafluorophosphate ion typically exploit one or more of the following properties: that it is a non-coordinating anion; that hexafluorophosphate compounds are typically soluble in organic solvents, particularly polar ones, but have low solubility in aqueous solution; or, that it has a high degree of stability, including resistance to both acidic and basic hydrolysis.

The main commercial use of hexafluorophosphate is as its lithium salt, lithium hexafluorophosphate. This salt, in combination with dimethyl carbonate, is a common electrolyte in commercial secondary batteries such as lithium-ion cells. This application exploits the high solubility of hexafluorophosphate salts in organic solvents and the resistance of these salts to reduction by the alkali metal cathode.[17] Since the lithium ions in these batteries are generally present as coordination complexes within the electrolyte,[18] the non-coordinating nature of the hexafluorophosphate ion is also a useful property for these applications.

Hexafluorophosphate salts are often included in organometallicsyntheses to provide an inert and non-coordinating counterion. Tetrafluoroborate salts are a common alternative choice. One route to such compounds involves reactions with silver hexafluorophosphate with the halide salt. Precipitation of insoluble silver halide salt helps drive this reaction to completion. Since hexafluorophosphate salts are often insoluble in water but soluble in polar organic solvents, even the addition of ammonium hexafluorophosphate (NH4PF6) to aqueous solutions of many organic and inorganic salts gives solid precipitates of hexafluorophosphate salts. This method can have advantages over the silver hexafluorophosphate method in terms of expense and in systems where contamination with metal ions is strongly discouraged. As an example, the microwave synthesis[19] of rhodicinium hexafluorophosphate involves the reaction of cyclopentadiene and rhodium(III) chloride hydrate in methanol. During the workup with methanolic ammonium hexafluorophosphate the product salt precipitates cleanly from the reaction mixture.[20] The overall conversion equation is

Whilst the hexafluorophosphate ion is generally considered inert and hence a suitable counterion, solvolysis reactions of the hexafluorophosphate ion are known. For example, the tris(solvent) rhodium complex [(η5-C5Me5)Rh(Me2CO)3](PF6)2 undergoes solvolysis when heated in acetone, forming a difluorophosphate-bridged complex [(η5-C5Me5)Rh(μ-OPF2O)3Rh(η5-C5Me5)]PF6.[21][22]

Hexafluorophosphate organic salts that are soluble in organic solvents and ionic liquids are well known. The routes to such compounds are similar to those used for organometallic salts, such as anion exchange from the halide salt with silver hexafluorophosphate or use of ammonium hexafluorophosphate. Room temperature ionic liquids such as 1-butyl-3-methylimidazolium hexafluorophosphate (typically abbreviated as bmimPF6) have been prepared.[23] The advantage of the anion exchange in favour of a non-coordinating anion is that the resulting ionic liquid has much higher thermally stability. The reason is that the possibility of decomposition of the imidazolium cation is decreased; 1-butyl-3-methylimidazolium chloride could decompose to N-methylimidazole and 1-chlorobutane or to N-butylimidazole and chloromethane. Such decompositions are not possible for bmimPF6 However, thermal decompositions of hexafluorophosphate ionic liquids to generate hydrogen fluoride gas are known.[5]

The hexafluorophosphate ion, being a large anion, can be useful in stabilising large cations. In the compound tetrakis(acetonitrile)copper(I) hexafluorophosphate, [Cu(CH3CN)4]PF6, the acetonitrileligands protect the copper(I) centre from oxidation to copper(II);[dubious– discuss] combined with the lability of the complex, this makes for a suitable precursor in the non-aqueous syntheses of copper(I) compounds.[24] However, the nearly linear arrangement of the 'arms' of this tetrahedral cation makes for a high degree of bulk.[25] Consequently, the inclusion of a bulky counterion has a stabilising effect and a non-coordinating anion like hexafluorophosphate is ideal given the lability. The compound can be produced by the addition of hexafluorophosphoric acid to a suspension of copper(I) oxide in acetonitrile:[24]